Detergent composition and method



Patented Oct. 23, 1945 DETERGENT COMPOSITION AND METHOD OF MAKING SAMELawrence H. Flett, Hamburg, N. Y., assignor to Allied Chemical & D

tion of New York ye Corporation, a corpora- No Drawing. Application July21, 1941, i Serial No. 403,456

12 Claims.

This invention relates to improvements in the manufacture of detergents,more particularly to improvements in the manufacture of alkyl arylsulfonate detergents.

, It has been found that water-soluble alkyl aryl sulfonates havesurface-active properties which.

make them suitable for use as wetting agents. Such sulfonates may beprepared by alkylating an aromatic compound such as benzene,naphthalene, phenol and the like to form a nuclear alkyl aryl compound,sulfonating this compound and neutralizing the sulfonic acid with anal-' kaline material to yield the desired sulfonate. I have disclosed inmy copending application Serial No. 93,521, filed July 30, 1936, issuedMay 19, 1942, as Patent No. 2,283,199, that a preferred method ofmanufacturing substances of this type involves halogenating a. suitablepetroleum distillate comprising for the most part a mixture of aliphatichydrocarbons, condensing the halogenated distillate with an aromaticcompound in the presence of a condensin agent such as aluminum chloride,and then sulfonating the alkyl aryl compound thus produced' I havefound, however, that such alkyl aryl sulfonates, particularly alkyl arylsulfonates the alkyl side chains of which are derived from petroleumdistillates, have relatively little effective washing action whenemployed in soft water for washing woolens, and to my knowledge nocommercially successful I have made the surprising discovery that alkylaryl sulfonate compositions having excellent detergent properties may beobtained by incorporating carefully controlled amounts of water-solublealkali, alkaline earth or ammonium salts with one or more alkyl arylsulionates, the alkyl side chains of which havetan average carboncontent detergent of the alkyl aryl sulfonate type with of at least 12and not more than 16 carbon atoms, so as to form a compositioncontaining between and of the salt. A preferred embodiment of myinvention involves improving the detergency of mixtures of alkyl arylsulfonates, the alkyl side chains of which are derived from petroleumdistillates containing hydrocarbons having an average carbon content ofat least 12 and not more than 16 carbon atoms per molecule, e. g.kerosene fractions, by the incorporation therein of water-solublealkali, alkaline earth or ammonium salts in the amounts indicated; thus,in accordance with this preferred embodiment the alkyl side chain of thealkyl aryl sulfonate treated may, for example, be' derived frompetroleum distillates, the lower boiling points of which are not belowC, at atmosphericpressure and the upper boiling points of which are notmore than 350 C. at 25 mm. of mercury absolute pressure, the bulk of thedistillate boiling over a range of 180 to 300 C.; such distillates maybe suitably derived from Pennsylvania or Mt. Pleasant, Michigan,petroleum. (For convenience, when the alkyl side chain of the sulfonatecomposition which is treated in accordance with my invention is derivedfrom a kerosene, the side chain is referred to as a keryl side chain.)The improvement in the detergency of such alkyl aryl sulfonates efiectedby my invention is particularly surprising, since these substances whennot admixed with a salt of the above-mentioned type do not efiectivelyremove solid soil from woolens or other textiles in soft water; theproducts of my invention, on theother hand, have been found tobeparticularly effective detergents, especially for woolens, in softwater. Thus, it is evident my invention constitutes an important advancein the alkyl aryl sulfonate field. 1 l

The importance of correlating the length of the alkyl side chain of thealkyl aryl sulfonate with the amount of salt present in the sulfonatecomposition in order to achieve improved detergent action was notrealized by the art prior to this invention. Ingenerai, the solubilityin water of alkyl aryl sulfonates decreases as the number of carbonatoms in the alkyl side chain increases. It has been pointed out byUnited States Patent 1,836,588, issued to Gunther December 15, 1931,that the wetting and emulsifying action of alkyl aryl sulfonates havingrela tively short alkyl side chains, such as, for example, butylatednaphthalene sulfonate, are improved by the addition thereto ofsubstantial amounts of water-soluble salts, the inference from thispatent being that the reater the proportion of salt, within practicallimitations, the more effective is the product obtained. However, theaddition of such salts does not generally improve the wetting oremulsifying action of alkyl aryl sulfonates containing 12 or more carbonatoms in the alkyl side chain, but in ssome cases actually impairs thewetting and emulsifying action of such products. It has also been foundthat when employing aqueous solutions of alkyl aryl sulfonates, thealkyl side chains of which are relatively long, e. g. 18 to 20 carbonatoms, the addition thereto'of substantial amounts of a salt such assodium sulfate causes the sulfonate to recipitate from the solution inan objectionable form and thus destroy any desirable surface action ofthe sulfonate. In view of these facts it was not to be expected thatalkyl aryl sulfonates, the alkyl side chains of which have a carboncontent falling within the limited range of 12 to 16 carbon atoms,admixed with a controlled amount of a salt of the above type, such assodium sulfate or sodium chloride, would be capable of exertingexcellent detergent action and would, in particular, be highly effectivefor washing woolens in soft water; and these qualities of mycompositions are the more surprising when it is realized that suchexcellent detergent action is not shown by alkyl aryl sulfonates withmore orless carbon atoms in the alkyl side chains than are present inthe alkyl groups of the alkyl aryl sulfonates of my compositions, andthat the added salt in my compositions does not enhance their wettingaction and seriously injures their emulsifying action.

In carrying out my invention, the amount of the water-soluble alkali,alkaline earth or am-' monium salt incorporated with the alkyl arylsulfonate must be carefully controlled. The incorporation ofsubstantially more than 65% of such water-soluble salts considerablyimpairs the effective detergency of the sulfonate} on the other hand,incorporation of less than 40% of such salts in compositions of thistype does not develop the desired washing action. Only by carefullycontrolling the amount of water-soluble salts incorporated in thecomposition .so that the final composition contains between 40% and 65%thereof may the maximum detergent action of the sulfonate be achieved. j

I have found that the compositions of my invention are more friable andwhen in granular or flake form show a reduced tendency to egglomerateinto larger particles or to absorb moisture from the air than the puresulfonates; the compositions of my invention also have a lighter colorthan the pure sulfonates and are more easily manufactured because theycan be dried more quickly than the pure sulfonates. Furth rmor theincorporation of such water-soluble salts in the compositions of myinvention considerably reduces the final cost of the product whileincreasing their utility as washing agents. 'ihese factors all.contribute toward making my compositions of pre-eminent value in thedetergent field.

The alkyl aryl sulfonates which may be treated in accordance with myinvention may be any one or a mixture of alkyl aryl sulfonates, thealkyl side chains of which contain at least 12 and not more than 16carbon atoms, preferably at least 12 and not more than 15 carbon atoms.Thus, the aromatic'nucleus of the sulfonate may be derived from benzene,toluene, naphthalene, phenol, naphthols, phenetole and similar aromaticcompounds but preferably is derived from benzene. The alkyl side chainmay be either straight or branched, but my invention is particularlyeffective when the side chain is branched. These alkyl groups may bederived from any suitable alkylating agent containing the desired numberof carbon atoms, including, for example, non-aromatic alcohols such asprimary monohydric alcohols, secondary monohydric alcohols, tertiaryalcohols of all types, etc., olefin hydrocarbons, e. "g. polymerizedlower oleflns, or halogenated derivatives of substantially saturatedaliphatic hydrocarbons, by methods of condensing such alkylating agentswith aromatic compounds well known in the art. As hereinabove noted, thealkyl aryl sulfonates preferably treated in accordance with my inventionmay be prepared by halogenating petroleum dlstillates of thePennsylvania or Mt. Pleasant, Michigan, type having a boiling rangebetween about 180 and 300 C. and containing hydrocarbons having anaverage carbon content of at least 12 and not more than 16, andpreferably at least 12 and not more than 15, carbon atoms per molecule,condensing the halogenated hydrocarbon mixture with an aromatic compoundin the presence of aluminum chloride and sulfonating the alkyl arylcompound thus produced to yield the desired salts are generallycharacterized by having a poor surface tension depressant action. Thus,for example, sodium, potassium, lithium and ammonium sulfates, sulfites,thiosulfates, chlorides, phosphates, borates, and acetates may beadvantageously employed in the practice of this invention. Alkali metalsulfates and chlorides are preferred, sodium sulfate and sodium chloridebeing particularly suitable for incorporation in detergent compositionsof my invention.

The incorporation of a water-soluble salt with the alkyl aryl sulfonateto furnish the improved detergents of my invention may be accomplishedby merely adding the salt to salt-free sulfonate or in a variety ofother manners. One method of effecting this incorporation which may beemployed when the'presence of a sulfate in the final composition is notobjectionable involves sulfonating the alkyl aryl compound from whichthe sulfonate is prepared with an excess of sulfuric acid over theamount required for the sulfonation, so that upon neutralization of thesulabout 65% of the final composition. However,

this method is obviouslylimited to-the preparamHate-andahus -.beemployed r gm acid, separating the siflforiic Iacid .I'i'rom' the:uns'ulfonated impurities-and from "the excess sulfonating agent,neutralizing the acid and then inmmatiomofifmexamiflfiwmmmdmwphatesa'riitli rthe -sulfofiate.' Another preferred method of obtaining thecompositions of my invention involves sulfonatthealkyl aryl-compound-toform the sulronic toistandto separate the acid which was with- :drawnand discarded.

" The I acid-washed. fkeryllii-benz'ene- "niixed-wlth' aboutT1l25-.timesi its weight off-100% snlfuric acid at atemperatur'e between 30 and35, the mixture warmed to 55 and agitated at that temperature for onehour. It was thenpermittedito' stand for two hours. during -.which time*threedayers of material separatedgthe upper mixing therewith thedesired amount of the Y water-soluble salt to be added; the solutionthus formed may then be dried to yield the desired composition.Furthermore, salt-free alkyl aryl sulfonates may be prepared bysulfonating the alkyl aryl compound with an excess of sulfuric acid,neutralizing the sulfonation mass, removing the inorganic salt from theneutralized mass by solution in alcohol, in which the alkyl arylsulfonate is soluble, and the desired water-soluble salt then added tothe salt-free sulfonate. It is to be understood that the sulfonic acidmay be neutralized with a mixture of bases, if desired,

and that the added salt need not have the same cation as that of thesulfonate.

The followin examples are illustrative of the composition of myinvention. Amounts are given in parts by weight and temperatures in derees centigrade. I

EXAMPLE 1 Part 1.10,620 parts of Pennsylvania kerosene having an averagecarbon content of 13 to 14 carbon atoms per molecule and a boiling rangeof from 185 to 275 were charged into a leadlined kettle and warmed toabout 60, 4.4 parts of iodine were dissolved therein and chlorine gaspassed through the kerosene, which was maintained at a temperaturebetween 60 and 70, at an average rate of about 300 parts per hour untilthe specific gravity of the" chlorinated kerosene amounted to 0.918 at24.

Part 2.To a mixture of 13,272 parts of benzene and 332 parts ofanhydrous aluminum chloride, 6,636 parts of the chlorinated keroseneprepared as described in Part 1 were added with agitation over a periodof about three hours; during the addition the temperature of the massrose to about 35. When all the chlorinated kerosene had been added themixture was heated to 45 and maintained at this temperature for about 1/2 hours; at the end of this time agitation was stopped, the masspermitted to stand and the lower tarry layer withdrawn. The upper layerwas stripped of its low-boilin hydrocarbons by distilling the liquid at150 first under atmospheric pressure, and finally under reduced pressureat, about '3 or 4 inches of mercury absolute. The stripped material wasthen vacuum distilled until about 7% of the charge in the still had beenremoved as distillate; the residue was further distilled and thedistillate therefrom collected layer consisting chiefly of unsulfonatedmaterial, the middle layer of sulfonated keryl" benzene, and the lowerlayer of spent sulfuric acid. The middle layer was separated from theother layers, drowned. in ice water and neutralized with an aqueoussolution of sodium hydroxide. The solution thus obtained containeddissolved therein a composition consisting chiefly of 63% sodium kerylbenzene sulfonate and 37% sodium sulfate. 8,590 parts of sodium sulfatewere then dissolved in this solution and the resulting solution dried ona drum drier. The resulting product contained about 61.3% sodium sulfateand had excellent washing properties.

EXAMPLE2 Pairt 1.-A Pennsylvania petroleum distillate (kerosene), whichdistilled from about 200 to about 266, and of which about 80% distilledover the range ofabout 220 to 260, and which comprised substantially amixture of hydrocarbons which were chiefly aliphatic and saturated andhad an average carbon content of 12 to 15 carbon atoms per molecule, waschlorinated at about by passing through it a stream of chlorine gasuntil the chlorinated mixture had increased in weight by about 20%because of organicallycombined chlorinetherein. The resulting mixture ofunchlorinated and chlorinated hydrocarbons was aerated to removepractically all dissolved hydrogen chloride. The chlorinatedhydrocarbons in the mixture contained a preponderant amount of monochlorhydrocarbons.

Part 2. 30 parts of anhydrous aluminum chloride were added slowly to anagitated mixture of 200 parts of benzol and 300 parts of the chlorinatedmixture prepared as described in Part 1. The mixture was cooledexternally until the vigorous evolution of hydrogen chloride gases fromthe mixture had abated. 'It'was then heated and maintained at itsrefluxing temperature for about one hour, or until the evolution ofhydrogen chloride had ceased. The reaction' mass was then'cooledanddrowned with a mixture of about 400 parts of crushed ice; 200,partsof water and 50 parts of commercial muriatic acid, the mixturepermitted to stratify, and the organic oily layer separated, washed witha small amount of water, and distilled. 'Theportion which distilled fromabout 160 to about 210 at/i mm. of mercury pressure, wascollected; itconsisted of a mixture of alkylated benzene's'in which the 'alkyl groupsa test portion, after neutralizing with sodium containedpredominantly-from about 12 to about 15 c r on iat slw;

,Part"3.- =l00iparts of the distilled oil obtained according tojPIa rt'2 of this example were mixed with parts of 20% oleum at a temperature ofapproximately 10. The mixture was permitted to warm to25 to 30 and wasstirred at this temperature fO1' 1 /2 to 3 hours, or until one part ofhydroxide, was soluble in 20 parts of water. The mixture was then pouredinto approximately 600 parts ofanice-water mixture, and the resultingsolution made neutral to Brilliant Yellow and Congo red papers withsodium hydroxide. The neutralized solution was evaporated to dryness ona rotary drum drier. The product obtained was in the form of light-buffto white flakes. It comprised chiefly a mixture of alkyl benzenesulfonates and alkali metal sulfate and contained about 50% of thesulfate; its aqueous solutions had excellent washing properties.

EXAMPLE 3 Part 1.--150 parts of a crude chlorinated kerosene prepared asdescribed in Example 2, Part 1, 90 parts of naphthalene, and 25 parts ofanhydrous zinc chloride were thoroughly mixed and heated to about 135 ina reactor fitted with a reflux condenser. The mixture was kept at about135 for about 45 minutes or until the evolution of hydrogen chloride hadpractically ceased. The reaction mixture was then cooled, mixed withwater, permitted to settle and the upper (organic) layer withdrawn andwashed with water until reasonably free from water-soluble products. Thewashed organic liquid mass was distilled in vacuo, and the fractionwhich distilled between 145 and 250 at a pressure of 8 to 12 mm. ofmercury was collected.

Part 2.--l parts of the distilled oil obtained according to Part 1 ofthis example were treated, with good stirring, at with 120 parts of 7%oleum. The mixture, while being stirred, was then permitted to Warm upto 25 to 30 and maintained at that temperature for 1 to 2 hour, or untila neutralized test portion was soluble in twenty times its weight ofwater. The sulfonation mixture was then drowned in three times itsweight of an ice-water mixture and the resulting solution neutralizedwith caustic soda and evaporated to dryness, as in Example 2, Part 3.The product was in the form of light-butt to white flakes. It comprisedchiefly a mixture of sulfonates of alkyl naphthalenes and about 50%sodium sulfate. Its aqueous solutions had good washing properties.

EXAMPLE 4 Part 1.'A kerosene fraction of Pennsylvania. petroleum boilingfrom 185 to 280 was fractionated and a fraction collected between 91 at13 mm. pressure and 109 at 12 mm. pressure. The collected fractionboiled from 200 to 235 at atmospheric pressure and 90% of it boiledbetween 21215" and 231; it had an average carbon content of 12 to 13carbon atoms per molecule. Chlorine was then passed into 340 parts ofthis fraction at a temperature below 60, in the presence of light,.untilthere was an increase in weight of 88 parts.

Part 2.150 parts of the-chlorinated mixture produced in Part 1 of thisexample were added, with agitation and as rapidly as possible, to amixture of 80 parts of benzene and 4 parts of ,anhydrous aluminumchloride at ordinary temperatures.

EXAMPLE5 Part 1.173 parts of chlorinated kerosene,

, prepared by chlorinating a Pennsylvania kerosene fraction boilingbetween 220 and 240 and having an average carbon content of 12 to 14carbon atoms per molecule until the weight of the kerosene had increasedby about 20% due to organically combined chlorine, were mixed with 1'75parts of phenol and 150 parts of zinc chloride and the mixture refluxedwith agitation at a temperature of about 135 until the evolution ofhydrogen chloride gas had ceased. The mass was then further heatedunder. reflux at a temperature of about 175 for about 16 hours. At theend of this time the mass was permitted to cool, was diluted with water,and the insoluble oil washed with water until free of water-insolubleimpurities. The washed oil was then vacuum distilled and the fractionboiling between 185,

and 210 at 8 mm. pressure was collected separately.

Part 2.--.56 parts of 100% sulfuric acid were slowly added to 50 partsof the keryP' phenol thus obtained, care being taken to maintain thetemperature below 30 during addition of the acid. When all the acid hadbeen added, the mass was warmed to and held at that tern-'- perature forabout twenty minutes until a test sample was completely soluble inneutral, acid and alkaline water and/or did not precipitate calciumsalts from a calcium chloride solution containing the equivalent of0.224 gram-of cal-.

cium oxide per liter. The mass was then diluted with water'andneutralized with sodium hydroxide; the neutral solution of the sulfonatewas filtered and drum dried; The final keryP' phenol sulfonate productcontained about 55% sodium sulfate and its solutions had excellentwashing properties.

EXAMPLE 6 parts of commercial cetyl alcohol, (containing 30% to 40% ofnormal cetyl alcohol, 30% to 40% of higher alcohols than cetyl, e. g.stearyl alcohol, etc., about 10% of normal lauryl alcohol and about 20%of normal myristyl alcohol), 100 parts of phenol, and '100 parts ofanhydrous zinc chloride were heated at to 180, under a reflux condenser,with agitation for sixteen hours. The condensation product was washedwith water until practically free from water-soluble,products. Theresulting oil was fractionally distilled in vacuo. The fraction or thedistillate which was to 118 at 10 mm. pressure and containing residuaibenzene was separated from the remainder which comprised a mixture ofalkyl benzene and residual kerosene.

Part 3.-75 parts of the alkyl benzene product CHl in which Rm is astraight-chain hydrocarbon radical having the formula:

CioHn, C12H25, C14H2a or Ciel-Is:

the compound in which Rm is C14H2o being a predominating compound, witha small amount of normal alkyl phenols and probably some ortho isomerspresent.

100 parts of the resulting purified alkyl phenol mixture, 40 parts ofacetic anhydride and 106 parts of sulfuric acid monohydrate were mixedtogather and warmed gentlyto 70 to 75 until the product was completelysoluble in water and a neutral 0.2% solution did not precipitate calciumsalts from a calcium chloride or other soluble calcium salt solutioncontaining the equivalent of 0.224 gram calcium oxide per liter. Themass was diluted with water to a final volume of 450 to 600 7 in waterto give brown to water-white solutions.

It comprised a mixture of inorganic salts (e. g. sodium salts) withsulfonates of the said alkyl phenols (e. g. in the form of the sodiumsalts),

of which mixture the inorganic salts constituted in the neighborhood of60%. The alkyl phenol sulfonates present were soluble in alcohol,benzene and other organic solvents.

EXAMPLE '7 533 parts of Pennsylvania kerosene, boiling over the range208 to 280 at atmospheric pressure with 80% distilling within the range233 to 267 and having an average carbon content of 13 to 15 carbon atomsper molecule, were charged into a lead-lined vessel. 0.25 part of iodinewas dissolved in the kerosene with agitation, and a stream of chlorinewas run therethrough at a rate of 40 to 50 parts of chlorine per hour.The temperature was held at 45 to 55 during chlorination, which wascontinued until the specific gravity of the chlorinated kerosene was0.920 at 24. 327 parts of this chlorinated kerosene and 164 parts ofphenol were then charged into a cast-iron jacketed kettle and 33 partsof anhydrous zinc chloride added thereto with agitation during the.course of ten minutes, the temperature being held below 50. The batchwas gradually heated to 160 over a period 'oftwo to three hours and heldat 160 for five hours with continued agitation. Heating was thendiscontinued, the agitation stopped, and the'batch permitted to settlefor at least four hours. The oil layer (crude "keryl phenol) was thendrawn of! from the zinc chloride settlings which were discarded.

The crude keryl phenol was then charged to a suitable kettle andstripped under reduced presagitation, the temperature being held at 80to 90. The mass was then gradually heated to 135 over a period of aboutthree hours, a slight vacuum (1-3 inches of mercury) being maintained.The vacuum was then released and the batch cooled to 110. 239 parts ofwater were added and about 5 parts of 50 B. sulfuric acid were run inuntil a strong acid reaction was obtained. After agitating at 80 to 90for fifteen minutes, the agitation was stopped and the mass permitted tostand for about one hour. The lower aqueous layer was drawn oif anddiscarded.

The water-insoluble oil (crude keryl phenetole) was treated with a smallamount of caustic I anddried by heating to 110 to 120 under slightlyreduced pressure (3-5 inches of mercury vacuum).

The crude dried kery phenetole was then charged into a still, togetherwith 1% of its weight of flake caustic soda, and distilled under reducedpressure. Samples of the distillate were collected and tested forsolubility in an equal volsure. The stripping was stopped when the vapormass over a period of one hour with continued ume of sulfuric acid. Whenthe vapor temperature in degrees centigrade was equal to plus theabsolute'pressure in millimeters of mercury, a test sample of thedistillate was soluble in 100% sulfuric acid to the extent of,10%.

The distillate collected up to this point was discarded. Distillationwas continued and the distillate collected until the vapor temperatureequaled 250 plus the absolute pressure in millimeters of mercury.

107 parts of the keryl phenetole fraction thus collected were chargedinto an enamellined kettle and 188 parts of 100% sulfuric acid wereslowly and evenly added over a period of one to two hours withagitation, the temperature being kept at 15 to 20. The batch was thenwarmed to 25 to 30 and agitation continued for three hours, at whichtime a' neutralized test sample was completely soluble in distilledwater.

The sulfonation mass thus obtained was run into an agitated mixture of167 parts of water, 800 parts of cracked ice and 1 part of disodiumphosphate, and the diluted mass neutralized with about 300 parts ofcaustic soda (50% solution), care being taken to keep the temperaturebelow 30. The neutralized solution was dried on a double drum drier,yielding a product consisting mainly of keryl phenetole sulfonate andabout 60% sodium sulfate.

In order to illustrate the improved detergent action oi thecompositionof my invention, the following series of detergent compositions wereprepared and tested as indicated in the subsequent examples.

EXAMPLE 8 Large batches of sodium keryl benzene sulfonate, sodium "kerylphenol sulfonate, sodium cetyl phenol sulfonate and sodium kerylphenetole sulfonate were prepared by processes similar to thoseillustrated in Examples 1, 5, 6 and '7 respectively. These products werethen each extracted with ethyl alcohol, whereby the sulfonate wasseparated from the sulfate and a salt-free.

detergent material was obtained; the ethyl alcohol solutions weredrumdried. Measured portions of these salt-free detergent materials werethen mixed with different proportions of anhydrous sodium sulfatedissolved in distilled water, and the resulting aqueous solutions weredrum dried. The products thus obtained constituted a series ofcompositions containing varying amounts 01' sodium sulfate admixed wtihan alkyl aryl sulionate.

Comparative washings with 02% aqueous soaasmvaj .TunlIV En'ect of sodiumsulfate on the washing power of solutions of sodium leery phenetolelutions of these compositions were then made in mu a Launderometer asfollows:

A sample of cloth was uniformly soiled with [Petergentcompositlon Woolwashing Woolwashing lampblack, tallow and mineral oil. It was then Mcut. into pieces of approximately equal size Soit 10 mm Soft lhard (4" x4") which were washed in a Launderometer in 200 cc. of solution forthirtyminutes at P geant Per on: AM] to b h 50. The degree of washingwas determined by h gg i g' 1 taking readings of reflected light(brightness) .selt V w Abwlgtebrlshtnw vi y fier with a Zeiss-Pulfrichphotometer; the readings gimmooififfi represent increased brightnesswhich is measured tennis oiper cent by the diiferences between thereadings obtained with the photometer on the soiled unwashed 3 5: gcloth and on the soiled cloth after-washing. The a 45 50 a2 20 4s 28results obtained by these tests are indicated in 38 13 54 F r thefollowing tables:

Team: I Enect of sodium sulfate on the washing power of solutions ofsodium "leery benzene sulfonate Detergent composition CottonwashingWoolwashlng Cotton washing Woclwashing Soit 10mm 80ft 10 bard son 10 mmSoft 10 hard m- PM. mt water water water water water water water watersol. organic g5 x salt t Absolute brightness in divided by Absolutebrightness increase -keryl" lsulfonate concentrations intanthso percent100 None 1.0 0.0 8.5 12.0 2.5 4.5 4.0 0.0 00 40 10.5 2110 20.0 22.0 1a:21.1 225 23.3 55 10.0 24.0 20.5 33.0 11.2 21.2 s22 30.0 to to 20.1: 24.020.0 31.5 20.0 24.0 1 32.0 21.5 40 22.0 23.5 21.0 21.0 ns 20.2 20.0 41.140. 00 20.0 21.5 28.0 42.0 25.0 20.0 220 53.1 35 05 10.0 22.0 20.0 23.021.1 21.5. 41.4 41.2

TAB n It will be noted from the above tables that the presence of thesodium sulfate markedly in- Efiect of sodium sulfate on the washingpower of solutions of sodium "leery? phenol sulfonate Detergentcomposition Wool washing Wool washing son 10 hard sou 10 hard waterwater water water Per cent Per cent V sol. sol. Absolute brightorganicinorganic ness increase disalt salt Absolute brightness videdbykeryl"increase aryl sulionate. concentratlonsin V tenths oi'per cent 100 None24 10 i2 i0 55 46 33 29 30 26 45 65 29 18 32 20 'I'ABLI III Efiect ofsodium sulfate on the washing power creased the washing power of thesulfonate. While in some cases the absolute brightness increase observedin connection with the use of compositions containing-sodium sulfate wasnot much greater or even slightly less than the absolute increase whenemploying pure sulfonate alone, it must be remembered that in such casesthe solutions contained a much lower concentration of the sulionate thanwhen the pure sulfonate was employed and, hence, in the absence of thesodium sulfate would have shown a much poorer detergent action per unitof pure sulfonate. In order to illustrate the fact that the addition ofsodium sulfate to alkyl aryl sulfonates, the alkyl side chains of whichcontain from 12 to 16 carbon atoms, does not improve the wettingproperties of such sulfonates, the following example was carried out:

EXAMPLE 9 Sodium keryl benzene sulfonate and sodium cetyl phenolsulfonate were prepared by processes similar to those given in Examples1 and 6 above, respectively. These sulfonates were freed of inorganicsalts by extraction with alcohol and the alcohol solutions of thesulfonates drum dried. Solutions or these sulfonates containing varyingamounts of sodium sulfate were then made up and the wetting power ofthese solutions deter,

mined by preparing 500 cc. of the test solution,

placing the solution in a 600-cc. beaker maintained at 50", cupping a#10 canvas or'wool felt disc, 1" in'diameter, in a long-stem invertedrunnel, forcing the disc belowthe liquid level to a depth of 5 to 6 cm.and determining the time required ior the disc to fall out 01' thefunnel. The results of these tests are given in the fol-- lowing tables:

Tana: V

or application Serial No. 737,777, filed July 31, 1934,1ssued as UnitedStates Patent 2,196,985 of April 16,1940.

Efleot of added salt on abetting power of "leery? benzene sulfonatephenol sulfonate Composition tested Wetting time with cotton Wettingtime with wool canvas discs ielt discs tCilrtlipcsitiontCitzniiipotsition es e a cone. es e a cone. Pereent gompnsi' taken soas to Compositaken so as to aryl Sub 2E3 3? g? ii f keep1 (5011110. oition tebsed ketep (2011110. g

cety p one at ce p eno mate cone sulionate at a sufionate at" .1%

100 sec. 8O 11 sec. 55 9 see. 9 sec. 20 121 sec.. 8 see.

It will be noted that when the concentrations of the solutions testedwere adjusted so that the sulfonate concentration was constantthroughout the tests, the wetting-out time remained substantially thesame, indicating the added sodium sulfate did not improve the wettingproperties of the sulionates.

While the action of the water-soluble salts upon the detergent power ofthe alkyl aryl sulfonates tested in accordance with my invention is notclear, I believe that compositions. in which such salts have beenincorporated with the alkyl aryl sulfonates in the amounts indicatedtend to form solutions of a more colloidal nature upon being dissolvedin water than is the case when the saltiree sulfonates are dissolved inwater, due to a salting-out action exerted on the solution of thesulfonates by the salts; such colloidal solutions,

' I believe, are moreefiective detergents than the 691,082, filedSeptember 26, 1933, issued July 22,.

1941, as Patent No. 2,249,757; Serial No.'42,164, filed September 25,1935, issued February 3, 1942, as Patent No. 2,271,635; Serial No.93,521, filed July 30, 1936, issued May 19, 1942, as Patent No.2,283,199; which is in turn a continuation-in-part Since certain changesmay be made in the above compositions of matter and difierentembodiments of the invention could be made without departing from itsscope, it is intended that all matter contained in the above descriptionshall be interpreted as illustrative and not in a limitmg sense.

I claim:

1. An improved detergentcomposition comprising alkyl aryl sullfonates,the alkyl groups of which are derived from an aliphatic hydrocarbonmixture, the lower boiling point of which is not below C. at atmosphericpressure and the upper boiling point of which is not above 350 C. at 25mm. pressure, and a water soluble salt having an inorganic cationselected from the group consisting of water soluble sulfates, sulfltes,thiosulfates; chlorides, dihydrogen phosphates, borates and acetates,the amount or said watersoluble salt having an inorganic cation beingsuch that the sulfonate-salt mixture contains between about 40% andabout 65% by weight thereof.

2. An improved detergent composition comprising alkyl aryl sulfonates,the alkyl side chains of which are derived from a kerosene fraction atleast 80% of which boils within the range 180 to 300 0., and a watersoluble salt having an inorganic cation selected from the groupconsisting of water soluble sulfates, sulfites, thiosuliates, chlorides,dihydrogen phosphates, borates. and acetates, the amount of saidwater-soluble salt having an inorganic cation being such that thesulfonate-salt mixture contains between about to 300 0., and sodiumsulfate in an amount such that the sulfonate-sodium sulfate mixturecontains between about 40% and about 65% by weight thereof.

4. An improved detergent composition comprising alkyl benzenesulfonates, the alkyl side chains oi which are derived from a kerosenefraction at least 80% of which boils within the range 180 to 300 (2.,and a water soluble salt having an inorganic cation selected from thegroup consisting of water soluble sulfates,.sulfites, thiosuli'ates.chlorides, dihydrogen phosphates, borates and acetates, the amount ofsaid water-soluble salt having an inorganic cation being such that thesulfonate-salt mixture contains between about 40% and about 65% byweight thereof.

5. An improved detergent composition comprising alkyl benzenesulfonates, the alkyl side chains of which are derived from a kerosenefraction containing hydrocarbons'having an average carbon content of atleast 12 and not more than 16 carbon-atoms per molecule, at least 80% ofwhich boils within the range 180' to 300 C., and between 40% and about65% by weight sodium sulfate.

6. A method for obtaining improved alkyl benzene sulfonate detergentcompositions, which comprises incorporating with allnvl benzenesulfonates. the alkyl side chains of which are derived i'rom a kerosenefraction containing hyabout 40% and about 65% by weight thereof, saidincorporation being eifected by sulfonating the alkyl benzene compound,removing unsulionated materials and excess sulfonating agent from themass, neutralizin the sulfonic acid and adding the sodium sulfate to thesulfonate.

Y 8. A methodfor obtaining improved alkyl benzene sulfonate detergentcompositions, which comprises incorporating with alkyl benzenesuli'onates, the alkyl side chains of which are derived from akerosened'raction containing hydrocarbons having an average carboncontent of at least 12 and not more than 16 carbon atoms per molecule,at least 80% of which boils within the range of 180 to 300 0., sodiumsulfate in an amount such that the-mixture formed contains between about40% and about 65% by weight thereof, said incorporation being eifectedby sulfonating the alkyl benzene compound, neutralizing the sulfonationmass, separating the sulfonate from the mass and adding the sodiumsulfate to said sulfonate.

drocarbons having an average carbon content of at least 12 and not morethan 16 carbon atoms.

per molecule, at least 80% of which boils within the range of 180 to 3000., sodium sulfate in an amount such that the mixture formed containsbetween about and about 65% by weight of the sulfate, said incorporationbeing e fected by sulfonating the alkyl benzene with such an excess ofsulfonating agent that upon neutralization of the sulfonation mass saidmixture of sulfonate and sulfate is formed.

'7. A method for obtaining improved alkyl benzene sulfonate detergentcompositions, which comprises incorporating with alkyl benzenesulfonates, the alkyl side chains of which are derived from a kerosenefraction containing hydrocarbons having an average carbon content of atleast 12 and not more than 16 carbon atoms per molecule, at least 80% ofwhich boils within the range 180 to 300 (3., sodium sulfate in an amountsuch that-the mixture formed contains between 9. An improved detergentcomposition comprising, alkyl aryl sulfonates, the alkyl side chains ofwhich are derived from a kerosene fraction at least 80% of which boilswithin the range of 180 to300 C., and sodium chloride in an amount suchthat the sulfonate-sodium chloride mixture contains between about 40%and about by weight thereof.

10. An improved detergent composition comprising alkyl aryl sulfonates',the alkyl side chains of which are-derived from a kerosene fraction atleast of which boils within the range of to 300 0., and sodium acetatein an amount such that the sulfonate-sodium acetate mixture containsbetween about 40% and about 65% by weight thereof.

11. An improved detergent composition comprising alkyl benzenesulfonates, the alkyl side chains of which are derived from a kerosenefraction containing hydrocarbons having an average carbon content of atleast 12 and not more than 16 carbon atoms per molecule, at least 80% ofwhich boils within the range 180 to 300 C and between 40% and about 65%by weight sodium chloride.

12. An improved detergent composition comprising alkyl benzenesulfonates, the alkyl side chains of which are derived from a kerosenefraction containing hydrocarbons having an average carbon content of atleast 12 and not more 'than 16 carbon atoms per molecule, at least 80%of which boils within the range 180 to 300 C., and between 40% and about65% by weight sodium acetate.

LAWRENCE H. FLE'I'I.

